A collagen long-acting moisturizing soft hydrophilic contact lens material

Abstract

The present application belongs to the technical field of soft hydrophilic contact lenses, and provides a collagen long-acting moisturizing type soft hydrophilic contact lens material. The soft hydrophilic contact lens material of the present application comprises specific mass fractions of hydroxyethyl methacrylate, a comonomer, PDRN, a moisturizing component, an initiator and a crosslinking agent. The present application uses PDRN as the core bioactive component, which is highly homologous to the structure of human tissue collagen protein, has no risk of heterologous protein rejection, and significantly improves the biocompatibility of the substrate; the moisturizing component of PDRN is compounded with polyvinylpyrrolidone, glycerol and chitosan derivatives, the collagen moisturizing and high polymer water locking produce a synergistic effect, improve the long-acting moisturizing stability, reduce the adsorption and accumulation of tear protein, lipid and other sediments; the multi-component comonomer is compounded, laying a foundation for efficient water and moisture retention; the initiator system and the crosslinking agent system precisely control the network characteristics of the high molecular structure, and at the same time have wearing comfort and good mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of soft hydrophilic contact lens technology, and more particularly to a collagen-based long-lasting moisturizing soft hydrophilic contact lens material. Background Technology

[0002] Soft hydrophilic contact lenses (i.e., contact lenses) were originally used for vision correction. With continuous technological advancements, their applications have broadened, and the wearing time has correspondingly increased. However, soft hydrophilic contact lenses easily lose moisture during wear, leading to discomfort such as dry eyes, eye fatigue, and a foreign body sensation. In more severe cases, it can even cause eye diseases like dry eye syndrome. To improve their hydrophilic and moisturizing capabilities, most commercially available soft hydrophilic contact lenses use hydroxyethyl methacrylate (HEMA) as a hydrophilic monomer to create hydrogel-type lenses. Moisturizing components such as polyethylene glycol, edokine, and hyaluronic acid may also be introduced. For example, Chinese patent CN120699187A discloses a moisturizing contact lens with a hyaluronic acid coating. The contact lens material is immersed in a hyaluronic acid mixture, a crosslinking agent is added, and the mixture is cured and dried. The resulting moisturizing contact lens showed no significant dryness or discomfort after 150 minutes of wear. While the above solutions can improve the hydrophilicity and moisturizing ability of soft hydrophilic contact lenses, the improvement effect is still limited. Specifically: ① Hydroxyethyl methacrylate has poor intrinsic water retention capacity, and the water content of soft hydrophilic contact lenses decreases rapidly; ② Moisturizing components are usually chemical reagents with no biological activity, and can only achieve physical water locking. They cannot adapt to the physiological environment of the ocular surface, have poor biocompatibility, and may irritate sensitive individuals; ③ The lens surface easily adsorbs deposits such as tear proteins and lipids. Prolonged wear leads to increased deposit adsorption, causing eye discomfort.

[0003] Therefore, there is an urgent need to provide a long-lasting moisturizing soft hydrophilic contact lens material that can maintain good moisturizing properties even after prolonged wear, without causing obvious dryness or other discomfort. Summary of the Invention

[0004] The purpose of this invention is to provide a collagen-based, long-lasting moisturizing, soft, hydrophilic contact lens material to address the shortcomings of existing technologies.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a collagen-based long-lasting moisturizing soft hydrophilic contact lens material, comprising the following raw materials by weight: 100 parts of hydroxyethyl methacrylate, 3-10 parts of comonomer, 1-8 parts of PDRN, 2-12 parts of moisturizing component, 0.1-1.5 parts of initiator, and 0.05-1.2 parts of crosslinking agent.

[0006] Preferably, the comonomer comprises methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate.

[0007] Preferably, the mass ratio of methyl acrylate, methacrylic acid and hydroxypropyl methacrylate is 1:0.5~1.5:0.5~1.5.

[0008] Preferably, the moisturizing component comprises polyvinylpyrrolidone, glycerin, and chitosan derivatives.

[0009] Preferably, the mass ratio of the polyvinylpyrrolidone, glycerol and chitosan derivative is 1:1~1.8:0.3~0.8.

[0010] Preferably, the initiator comprises azodimethylpentanonitrile, benzoyl peroxide, and 2-hydroxy-2-methylphenylacetone.

[0011] Preferably, the mass ratio of azodimethylpentanonitrile, benzoyl peroxide and 2-hydroxy-2-methylphenylacetone is 1:0.1~0.5:0.2~0.7.

[0012] Preferably, the crosslinking agent comprises ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate.

[0013] Preferably, the mass ratio of ethylene glycol dimethacrylate, divinylbenzene and pentaerythritol tetraacrylate is 1:0.2~0.7:0.02~0.1.

[0014] The beneficial effects of this invention are: This invention uses PDRN as the core bioactive component, which is highly homologous to the structure of human collagen, eliminating the risk of rejection by foreign proteins. It combines moisturizing and biocompatibility, significantly improving the biocompatibility of the substrate and enhancing the fit of soft hydrophilic contact lenses compared to traditional heterologous collagen. The moisturizing components of PDRN, combined with polyvinylpyrrolidone, glycerin, and chitosan derivatives, create a synergistic effect between collagen moisturizing and polymer water-locking, breaking the limitations of traditional single physical or chemical moisturizing components. This improves long-term moisturizing stability, maintaining ocular surface moisture even after continuous wear for more than 12 hours without dryness or blurred vision, while reducing the adsorption and accumulation of tear proteins, lipids, and other deposits. Using traditional hydroxyethyl methacrylate as the core monomer, combined with multiple copolymer monomers, it lays the foundation for efficient water retention and moisturizing. The unique compound initiator system and crosslinking agent system precisely control the polymerization reaction process and the characteristics of the polymer network structure, effectively avoiding raw material residues. This allows the soft hydrophilic contact lenses to possess both wearing comfort and good mechanical properties. Detailed Implementation

[0015] This invention provides a collagen-based long-lasting moisturizing soft hydrophilic contact lens material, comprising the following raw materials by weight: 100 parts of hydroxyethyl methacrylate, 3-10 parts of comonomer, 1-8 parts of PDRN, 2-12 parts of moisturizing component, 0.1-1.5 parts of initiator, and 0.05-1.2 parts of crosslinking agent.

[0016] In this invention, the collagen long-lasting moisturizing soft hydrophilic contact lens material, by weight, comprises the following raw materials: 100 parts of hydroxyethyl methacrylate; 3-10 parts of comonomer, preferably 4-9 parts, more preferably 5-8 parts, and more preferably 6-7 parts; 1-8 parts of PDRN, preferably 2-7 parts, more preferably 3-6 parts, and more preferably 4-5 parts; 2-12 parts of moisturizing component, preferably 3-11 parts, more preferably 4-10 parts, and more preferably 6-8 parts; 0.1-1.5 parts of initiator, preferably 0.3-1.2 parts, more preferably 0.5-1 parts, and more preferably 0.7-0.8 parts; and 0.05-1.2 parts of crosslinking agent, preferably 0.1-1 parts, more preferably 0.3-0.8 parts, and more preferably 0.5-0.6 parts.

[0017] In this invention, the comonomer preferably comprises methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate. Hydroxyethyl methacrylate serves as the core monomer, providing the main framework. Methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate serve as comonomers, copolymerizing with the core monomer hydroxyethyl methacrylate to construct a three-dimensional polymeric network with high-density hydrophilic groups, thereby enhancing the intrinsic water retention capacity and oxygen permeability of the substrate.

[0018] In this invention, the mass ratio of methyl acrylate, methacrylic acid and hydroxypropyl methacrylate is preferably 1:0.5~1.5:0.5~1.5, more preferably 1:0.8~1.2:0.8~1.2, and even more preferably 1:1:1.

[0019] In this invention, the moisturizing component preferably comprises polyvinylpyrrolidone, glycerin, and chitosan derivatives. The moisturizing component enables the substrate to physically lock in moisture and provides long-lasting, sustained-release hydration. Combined with bioactive PDRN, it forms a triple moisturizing system of "physical water locking + collagen bio-moisturizing + long-lasting, sustained-release hydration," ensuring stable moisture content in the lens substrate and preventing rapid decline, thus significantly alleviating discomfort such as dryness and sensitivity.

[0020] In this invention, the glycerol is preferably medical grade glycerol, and the chitosan derivative preferably comprises one or more of carboxymethyl chitosan, quaternized chitosan, and acylated chitosan.

[0021] In this invention, the mass ratio of polyvinylpyrrolidone, glycerol and chitosan derivative is preferably 1:1~1.8:0.3~0.8, more preferably 1:1.2~1.7:0.4~0.7, and even more preferably 1:1.3~1.5:0.5~0.6.

[0022] In this invention, the initiator preferably comprises azodimethylvalerate, benzoyl peroxide, and 2-hydroxy-2-methylphenylacetone. The combined initiation system of thermal and photoinitiators achieves high polymerization efficiency. With proper dosage control, monomer and initiator residues can be significantly reduced, effectively avoiding the risk of eye irritation caused by residues.

[0023] In this invention, the mass ratio of azodimethylpentanonitrile, benzoyl peroxide and 2-hydroxy-2-methylphenylacetone is preferably 1:0.1~0.5:0.2~0.7, more preferably 1:0.2~0.4:0.3~0.6, and even more preferably 1:0.3:0.4~0.5.

[0024] In this invention, the crosslinking agent preferably comprises ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate. By selecting a crosslinking agent composed of ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate, and by controlling the dosage appropriately, the crosslinking network density of the monomer polymerization is optimized, so that the softness, mechanical strength, and deformation resistance of the lens are maximized and balanced.

[0025] In this invention, the mass ratio of ethylene glycol dimethacrylate, divinylbenzene and pentaerythritol tetraacrylate is preferably 1:0.2~0.7:0.02~0.1, more preferably 1:0.3~0.6:0.03~0.08, and even more preferably 1:0.4~0.5:0.04~0.06.

[0026] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0027] In the embodiments and comparative examples of the present invention, the glycerol is medical grade glycerol, and the chitosan derivative is carboxymethyl chitosan.

[0028] Example 1

[0029] By weight, the collagen-based long-lasting moisturizing soft hydrophilic contact lens material is composed of the following raw materials: The composition includes 100 parts hydroxyethyl methacrylate, 6 parts comonomer, 8 parts PDRN, 2 parts moisturizing component, 0.7 parts initiator, and 0.5 parts crosslinking agent. The comonomer is composed of methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate in a mass ratio of 1:1.5:1. The moisturizing component is composed of polyvinylpyrrolidone, glycerol, and chitosan derivative in a mass ratio of 1:1:0.5. The initiator is composed of azodimethylpentanonitrile, benzoyl peroxide, and 2-hydroxy-2-methylphenylacetone in a mass ratio of 1:0.5:0.2. The crosslinking agent is composed of ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate in a mass ratio of 1:0.7:0.04.

[0030] Preparation method of collagen long-lasting moisturizing soft hydrophilic contact lens: PDRN is dissolved uniformly in deionized water to obtain a collagen solution with a mass concentration of 20%. Hydroxyethyl methacrylate, comonomer, initiator, and crosslinking agent are mixed uniformly to obtain a monomer solution. The collagen solution and monomer solution are mixed, and then the moisturizing component is added and mixed uniformly to obtain a prepolymer solution. The prepolymer solution is transferred to a mold and crosslinked and set under ultraviolet light at 35℃ and a wavelength of 365nm for 25 minutes. Demolding yields the soft hydrophilic contact lens.

[0031] Example 2

[0032] By weight, the collagen-based long-lasting moisturizing soft hydrophilic contact lens material is composed of the following raw materials: The composition includes 100 parts hydroxyethyl methacrylate, 3 parts comonomer, 4 parts PDRN, 12 parts moisturizing component, 0.1 parts initiator, and 0.05 parts crosslinking agent. The comonomer is composed of methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate in a mass ratio of 1:1:1.5. The moisturizing component is composed of polyvinylpyrrolidone, glycerol, and chitosan derivative in a mass ratio of 1:1.3:0.8. The initiator is composed of azodimethylpentanonitrile, benzoyl peroxide, and 2-hydroxy-2-methylphenylacetone in a mass ratio of 1:0.3:0.7. The crosslinking agent is composed of ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate in a mass ratio of 1:0.2:0.1.

[0033] The preparation method of the collagen long-lasting moisturizing soft hydrophilic contact lens is the same as in Example 1.

[0034] Example 3

[0035] By weight, the collagen-based long-lasting moisturizing soft hydrophilic contact lens material is composed of the following raw materials: The composition includes 100 parts hydroxyethyl methacrylate, 10 parts comonomer, 1 part PDRN, 6 parts moisturizing component, 1.5 parts initiator, and 1.2 parts crosslinking agent. The comonomer is composed of methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate in a mass ratio of 1:0.5:0.5. The moisturizing component is composed of polyvinylpyrrolidone, glycerol, and chitosan derivative in a mass ratio of 1:1.8:0.3. The initiator is composed of azodimethylpentanonitrile, benzoyl peroxide, and 2-hydroxy-2-methylphenylacetone in a mass ratio of 1:0.1:0.4. The crosslinking agent is composed of ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate in a mass ratio of 1:0.4:0.02.

[0036] The preparation method of the collagen long-lasting moisturizing soft hydrophilic contact lens is the same as in Example 1.

[0037] Comparative Example 1

[0038] Replace 8 portions of PDRN in Example 1 with 10 portions of porcine type I collagen (molecular weight 300kDa), otherwise remain the same as in Example 1.

[0039] Preparation method of soft hydrophilic contact lens: Porcine type I collagen was dissolved uniformly in deionized water to obtain a collagen solution with a mass concentration of 20%. Hydroxyethyl methacrylate, comonomer, initiator, and crosslinking agent were mixed uniformly to obtain a monomer solution. The collagen solution and monomer solution were mixed, and then a moisturizing component was added and mixed uniformly to obtain a prepolymer solution. The prepolymer solution was transferred to a mold and crosslinked and set under ultraviolet light at 35℃ and a wavelength of 365nm for 25 minutes. Demolding yielded the soft hydrophilic contact lens.

[0040] Comparative Example 2

[0041] The comonomer of Example 1 is omitted, and everything else is the same as in Example 1.

[0042] Preparation method of soft hydrophilic contact lens: PDRN is dissolved uniformly in deionized water to obtain a collagen solution with a mass concentration of 20%. Hydroxyethyl methacrylate, initiator, and crosslinking agent are mixed uniformly to obtain a monomer solution. The collagen solution and monomer solution are mixed, and then a moisturizing component is added and mixed uniformly to obtain a prepolymer solution. The prepolymer solution is transferred to a mold and crosslinked and set under ultraviolet light at 35℃ and a wavelength of 365nm for 25 minutes. Demolding yields the soft hydrophilic contact lens.

[0043] Comparative Example 3

[0044] The difference from Example 1 is that the comonomer consists of N,N-dimethylacrylamide, N-vinylpyrrolidone and hydroxypropyl methacrylate in a mass ratio of 1:0.8:1.2.

[0045] Comparative Example 4

[0046] The difference from Example 1 is that the moisturizing component consists of sodium hyaluronate, polyethylene glycol 400 and edokine in a mass ratio of 1:0.3:1.2.

[0047] Comparative Example 5

[0048] The difference from Example 1 is that the initiator is 1.8 parts and the crosslinking agent is 1.5 parts. The initiator is composed of azodimethylpentanonitrile and benzoyl peroxide in a mass ratio of 1:0.8, and the crosslinking agent is composed of divinylbenzene and pentaerythritol tetraacrylate in a mass ratio of 1:0.9.

[0049] The performance of the soft hydrophilic contact mirrors prepared in Examples 1-3 and Comparative Examples 1-5 were tested respectively, and the test results are shown in Table 1. Among them, the water content was tested according to GB / T 11417.7-2012, and the oxygen permeability coefficient (DK) was tested according to the polarographic method in 4.4.3 of GB / T 11417.7-2012.

[0050] Table 1 Performance test results of soft hydrophilic contact mirrors

[0051] As shown in Table 1, the soft hydrophilic contact lenses of Examples 1-3 exhibit excellent water content and oxygen permeability, with a water loss rate of less than 5% after 12 hours of continuous wear. In contrast, Comparative Example 1, although its initial water content did not decrease significantly, showed a water loss rate of 7.5% after 12 hours of continuous wear, and a marked decrease in oxygen permeability. Comparative Example 2 omitted the comonomer and used hydroxyethyl methacrylate as the hydrophilic monomer, resulting in a significantly reduced initial water content and a water loss rate of 10.3% after 12 hours of wear, indicating a significant decrease in intrinsic water retention capacity and oxygen permeability. Comparative Example 3 used a comonomer composed of N,N-dimethylacrylamide, N-vinylpyrrolidone, and hydroxypropyl methacrylate, combined with the hydroxyethyl methacrylate core monomer. This combination improved the water content and oxygen permeability compared to the single hydroxyethyl methacrylate hydrophilic monomer, but still significantly lower than Examples 1-3. This demonstrates that the combination of the selected comonomer and the core monomer hydroxyethyl methacrylate in this invention yields superior results. Comparative Example 4, composed of sodium hyaluronate, polyethylene glycol 400, and edokine, synergistically moisturizes with PDRN. Under prolonged wear, its water loss rate is significantly higher than that of Examples 1-3, indicating that the moisturizing component of this invention can form an excellent synergistic moisturizing effect with PDRN, improving the intrinsic water retention capacity of the soft hydrophilic contact lens. Comparative Example 5, by altering the initiation and cross-linking systems, results in a change in the polymer network structure, failing to achieve excellent moisturizing and water-locking effects, and consequently, a significant decrease in water content and oxygen permeability.

[0052] As can be seen from the above embodiments, the present invention provides a collagen-based long-lasting moisturizing soft hydrophilic contact lens material. It uses hydroxyethyl methacrylate as the core hydrophilic monomer, combined with methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate as comonomers to form a multi-component copolymer system, laying the foundation for efficient water retention and moisturizing. PDRN is used as the core bioactive ingredient, which is highly homologous to the structure of collagen in human ocular surface tissue, eliminating the risk of foreign protein rejection and possessing both moisturizing and biocompatibility effects. Simultaneously, it works synergistically with the moisturizing components composed of polyvinylpyrrolidone, glycerin, and chitosan derivatives to improve long-lasting moisturizing stability and reduce the adsorption and accumulation of tear proteins, lipids, and other deposits. Specific initiation and cross-linking systems regulate the polymerization reaction and the characteristics of the polymer network structure, avoiding raw material residue. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material of the present invention can still maintain moisture and hydration after 12 hours of continuous wear, without dryness, sensitivity, or other discomfort.

[0053] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A collagen-based long-lasting moisturizing soft hydrophilic contact lens material, characterized in that, By weight, it contains the following ingredients: 100 parts of hydroxyethyl methacrylate, 3-10 parts of comonomer, 1-8 parts of PDRN, 2-12 parts of moisturizing component, 0.1-1.5 parts of initiator, and 0.05-1.2 parts of crosslinking agent.

2. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 1, characterized in that, The comonomers include methyl acrylate, methacrylic acid, and hydroxypropyl methacrylate.

3. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 2, characterized in that, The mass ratio of methyl acrylate, methacrylic acid and hydroxypropyl methacrylate is 1:0.5~1.5:0.5~1.

5.

4. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to any one of claims 1 to 3, characterized in that, The moisturizing components include polyvinylpyrrolidone, glycerin, and chitosan derivatives.

5. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 4, characterized in that, The mass ratio of polyvinylpyrrolidone, glycerol and chitosan derivative is 1:1~1.8:0.3~0.

8.

6. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 5, characterized in that, The initiator comprises azodimethylpentanonitrile, benzoyl peroxide, and 2-hydroxy-2-methylphenylacetone.

7. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 6, characterized in that, The mass ratio of azodimethylpentanonitrile, benzoyl peroxide and 2-hydroxy-2-methylphenylacetone is 1:0.1~0.5:0.2~0.

7.

8. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 6 or 7, characterized in that, The crosslinking agent comprises ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate.

9. The collagen-based long-lasting moisturizing soft hydrophilic contact lens material according to claim 8, characterized in that, The mass ratio of ethylene glycol dimethacrylate, divinylbenzene, and pentaerythritol tetraacrylate is 1:0.2~0.7:0.02~0.1.

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